Method for combating pests and preparations suitable therefor



able to ethers.

United States Patent Ofifi'ce Z ,8 6 l, 912 Patented Nov. 25, 1 958METHOD FOR COMBATING PESTS AND PREP- ARATIONS SUITABLE THEREFOR RichardSallmann, Binningen, Switzerland, assignor t Ciba Limited, Basel,Switzerland, a Swiss firm N0 Drawing. Application January 30, 1956Serial No. 561,976

Claims priority, application Switzerland September 25, 1951 11 Claims.(Cl. 167--22) The present application is a continuation-in-part of mygroup consisting of oxygen, nitrogen and sulfur, and Z is a memberselected from the group consisting of oxygen and sulfur.

Among the compounds of the above formula those in which the symbols X, Yand Z represent oxygen are most easily accessible. They correspond tothe general formula )PO-Ra R3O and can be made by methods in themselvesknown.

The aliphatic radicals, represented by the symbols R R and R may havestraight or branched chains and may be saturated or unsaturated.Moreover, they may be unsubstituted or may contain substituents. Theremay be mentioned for example, the following groups: Methyl, ethyl,propyl isopropyl, butyl, allyl, and 2-chlorethyl groups. The threeradicas R R and R may be the same or diiferent. For example there may bementioned the following compounds; trimethyl phosphite, triethylphosphite, tripropyl phosphite, tri-(2-chlorethyl) phosphite or theester of the formula CHz-O P -OC2Hs CH:O

The aromatic radicals which R and R may represent, may, if desired,contain nuclear substituents. There may be mentioned phenyl, or4-chlorophenyl, 2:4-dichlorophenyl, 4-methoxypheny1 or 4-nitrophenylgroups. There may be mentioned e. g. 2:4-dichlorophenyldiethyl phosphiteand 4-chlorophenyl-dimethyl phosphite.

For the purposes of 'the present invention compounds which are obtainedfrom phosphites of the above given formula wherein X, Y and Z representoxygen are prefer- Especially valuable are condensation products fromchloral and trial kyl phosphite and alkyl groups 2 of which contain 1 to4 carbon atoms. The most preferred compound is the condensation productfrom chloral and trimethyl phosphite.

The compounds used in the invention are obtained by reacting togetherthe aforesaid components in molecular proportions. They lead to unitaryproducts, and only one halogen atom enters into reaction,notwithstanding the possibility that two or three molecular proportionsof the phosphorus compound could react with one molecular proportion ofthe carbonyl compound. Since the reaction is frequently exothermic, itmay be necessary to react the components while cooling and to dilutethem with inert solvents, such as benzene, toluene, ether, dioxane,hexane or low boiling benzine. The reaction is advantageously brought toan end by heating up to about 50-120" C. By suitably choosing thereaction components the condensation products can be distilled underreduced pressure.

The constitution of the condensation products is probably RX O P-o 012-0R1Y and that of the trimethyl phosphite and chloral CHaO 0 P---CClz-CCHaO i) \H However isomeric formulae can be attributed to thecondensation products, like and In this formula R, R X, Y and Z have themeanings given above and n is zero or one. For the condensation productfrom trimethyl phosphite and chloral the formula is The compounds of theinvention are active against the various stages of development of thepests, such as eggs, larvae and imagines, so that they can be used ascontact, stomach or respiratory poisons.

'They are capable of protecting a very wide variety of materials againstpests, and gaseous or liquid or solid materials can be used as carriersfor the active substances. As materials to be protected or used ascarriers there come into consideration, for example, air, especially inrooms, and liquids such, for example, as water in ponds,

and finally any inanimate or living solid substratum such, for example,as any objects in living rooms, cellars, plaster floors, stables, andalso pelts, feathers, wool and the like, and also living organisms ofthe vegetable and animal kingdoms in their various stages ofdevelopment, insofar as they are insensitive to the pest-combatingagents.

The combating of pests may be carried out by the usual methods, forexample, by treatment of the material to be protected with the compoundsin vapor form, for example, as fumigating agents or in the form of dustsor spraying liquors, for example, in the form of solutions orsuspensions prepared with water or suitable organic solvents such. forexample, as alcohol, petroleum, tar distillates or the like. There mayalso be used aqueous solutions or aqueous emulsions of organic solventscontaining the active substances, for coating, spraying or impregnatingthe objects to be protected.

The spraying and dusting preparations may contain the usual inertfillers or identifying agents such, for example, as kaolin. gypsum orbentonite or other additions such as sulfite cellulose waste liquor,cellulose derivatives and the like. Furthermore, in order to improve thewetting or adhesive property the usual wetting agents or adhering agentsmay be added. The pestcombating preparations may be made in powderedform or in the form of aqueous dispersions or pastes or in the form ofself-dispersing oils.

The compounds may be present in the pest-combating preparations as thesole active substance or in combination with other insecticides and/ orfungicides. The use of such preparations for plant protection is carriedout by the usual spraying, dusting or fumigating methods. Suitablysubstituted compounds possess an intratherapeutic or so-called systemicaction on plants.

The following examples illustrate the invention, the parts being byweight unless otherwise stated, and the relationship of parts by weightto parts by volume being the same as that of the kilogram to the liter:

Example 1 In thisexample is described the preparation of a few of thecompounds used in the invention.

(1) A solution of 16.6 parts of triethylphosphite in 20 parts by volumeof benzene is added to a solution of 14.7 parts of chloral in 40 partsby volume of benzene. When the temperature no longer increases, thewhole is heated for one hour at 60-70 C., ethyl chloride being evolved.The solvent is then distilled off and the residue is fractionated invacuo. The condensation product boils uniformly at 85-86 C. under 0.05mm. pressure. The same product can be made without the use of a solvent,but in this case it is necessary to cool with a cooling mixture. Thechloral is then added dropwise at about --.5 C. while stirring, eachdrop producing a powerful reaction. In the same manner the condensationproduct from trimethyl phosphite and chloral can be obtained in the formof a colorless oil boiling at 85-87 C. under 0.2 mm. pressure. Thecondensation product from trilsopropyl phosphite and chloral boils at9697 C. under 0.1 mm. pressure and can be made in an analogous manner.Similarly, tri-(fl-chlorethyl)-phosphite can be reacted with chloral.

(2) A solution of 7.4 parts of chloral in 20 parts by volume of ether isadded dropwise to a solution of 6.8 parts of ethyl ethylene phosphite ofthe formula mixture is heated at the boil for 30 minutes. Afterdistlllmg off the ether there is obtained an oil which boils with slightdecomposition at 94-97 C. under 0.15 mm. pressure.

For the preparation of condensation products also the followingphosphite esters may be used CHzO\ P-OC2H5 (m-0 0H,

P-OC2H5 (311-0 CHzSCzHt CHr-O P-OCQH;

CH-O C lHzCl (Condensation product boils at 145-160 C. 10.3 mm. withdecomposition) CH1O (3) A solution of 8 parts of chloral in 5 parts byvolume of benzene is added to a solution of 14.1 parts of2:4-dichlorophenyl diethyl phosphite of the formula (nag-amount),

in 5 parts by volume of benzene. The reaction sets in immediately andthe temperature rises to 50 C. After the temperature has fallen, themixture is heated for one hour on the steam bath and then the benzene isdistilled olf in vacuo. By distilling the residue there is obtained aglycerine-like liquid boiling at 153-157 C. under 0.05 mm. pressure. Ina similar manner para-chlorophenyl diethyl phosphite orpentachlorophenyl diethyl phosphite can be caused to react.

(4) A solution of 7.4 parts of chloral in 10 parts by volume of benzeneis added dropwise while cooling with ice and stirring to a solution of11 parts of the compound of the formula (C2H5)2N in 20 parts by volumeof benzene. When all the chloral has been introduced, the stirringmechanism is stopped and the reaction mixture is allowed to stand for 30minutes at room temperature and for 90 minutes at 70- C. The benzene isthen distilled off and the residue is heated in vacuo on a steam bathuntil its weight remains constant. There are obtained 15.1 parts of ayellow-brown viscous oil. By using instead of chloral an equivalentquantity of trichloroacetic acid ethyl ester there is obtained a paleyellow colored oil boiling at 69 C. under 0.1 mm. pressure.

(5) 4.1 parts of chloral are added dropwise while cooling with ice to6.1 parts of the compound of the formula Q-lf-P (o 0 int),

5. ceases. After removing the volatile 90? C. in vacuo there lowish oil.

- (6) 4.5 parts of chloral are triethyl trithiophosphite while removingthe ice, the reaction sets in after a short time which is apparent fromthe increase in temperature and the evolution of gas. When thetemperature no longer increases, the mixture is heated for 30 minutes at60- 70 C. and the volatile constituents are distilled off in vacuo atthe same temperature. There are obtained 9.6 parts. of a yellowish oil.

constituents at 80- are obtained 6.8 parts of a yelmixed with 6.4 partsof cooling with ice. Upon Example 2 and 40 parts .of n-butanol. There isobtained a clear solution. This concentrated preparation can easily bediluted with water.

described above (=0.0 part percent product) aphides and red spiders canbe successfully combated.

Example 3 The preparation described in Example 2 is also active againstColorado beetles. sprayed with a (Musca domestica). Good activityagainst flies characterizes also the compounds described in Examples 1(3) and (4). I

Example 5 An insecticidal dusting powder can be prepared by mixing 1part of the condensation product from chloral and trimethyl phosphitewith 99 parts of talcum. By dusting areas which are infested with fliesand mosquitoes there is obtained a rapid killing of the insects.

Instead of talcum other carriers in powder form, e. g. bentonite, kaolinor mixtures thereof can be used. The amount of active ingredient can beincreased to 10 percent or more, or reduced to 0.1 percent or less.

it 0.5 part of the condensation product named above and 1 part of DDTare mixed with 98.5 parts of a powdered carrier, a dusting powder isobtained which exhibits a quick knock down and a long lasting effect.

2 parts of the condensation product named above, and 18 parts of copperoxychloride are mixed. This is a dusting powder which acts asinsecticide and fungicide.

The preferred forms of the pest combating compositions of the presentinvention are dusting powders and liquids which contain beside theactive ingredient a volatile organic solvent and a non-ionogenicemulsifying agent.

What is claimed is:

1. A method for combating insects which comprises applying to theobjects which are to be protected against the insects an insecticidalamount of a chloral-phosphite ester condensation product said productbeing prepared by adding together 1 mol of chloral and ,1 mol of aphosphite ester of the general formula \PZ-R| R1Y/ a saturated aliphaticradical containing 1 to 4 carbon atoms, X and Y are each a memberselected from the group consisting of oxygen, nitrogen and sulfur, and Zis a member selectedfrom the group consisting of oxygen and sulfur, thusforming a condensation product.

2. A method for combating insects which comprises applying to theobjects which are to be protected against the insects an insecticidalamount of a chloral-trialkyl phosphite condensation product saidcondensation product being formed by adding together 1 mol of chloraland 1 mol of a trialkyl phosphite the alkyl groups of which contain 1 to4 carbon atoms.

3. A method for combating insects which comprises applying to theobjects which are to be protected against the insects an insecticidalamount of the chloral-trimethyl phosphite condensation product saidcondensation product being formed by adding together 1 mol of chloraland 1 mo] of trimethyl-phosphite.

4. A method for combating insects which comprises applying to objectswhich are to be protected against the insects an insecticidal amount ofa chloral-phosphite ester condensation product; said condensationproduct being formed by adding together 1 mol of chloral and 1 mol ofphosphite ester of the general formula wherein each of R and Rrepresents a radical selected from the group consisting of saturatedaliphatic hydr0- carbon radicals containing 1 to 4 carbon atoms, phenylradicals and chlorinated phenyl radicals, R represents a saturatedaliphatic radical containing 1 to 4 carbon atoms.

5. A method for combating insects which comprises applying to objectswhich are to be protected against the insects an insecticidal amount ofa chloral-phosphite ester condensation product; said condensationproduct being formed by adding together 1 .mol of chloral and 1 mol ofphosphite ester of the general formula CH3O P-R CHyrO wherein Rrepresents a saturated aliphatic radical containing 1 to 4 carbon atoms.

6. A method for combating insects which comprises applying to theobjects which are to be protected against the insects an insecticidalamount of the composition which consists of 20 parts by weight of thetrimethyl phosphite-chloral condensation product, said condensationproduct being formed by mixing together equimolecular proportionsoftrimethyl phosphite and chloral, 49 parts by weight of the condensationproduct from 1 mol of octylphenol with 8 mols of ethylene oxide, and 40parts by weight of n-butanol.

7. A method for combating insects which comprises applying to theobjects which are to be protected against the insects an insecticidalamount of a dusting powder which consists of 0.1 to 10 percent by weightof the trimethyl phosphite-chloral condensation product, saidcondensation product being prepared by mixing together equimolecularproportions of trimethyl phosphite and chloral, and 99.9 to 90 percentby Weight of a powdered inert carrier.

8. An insecticidal composition of matter which consists of achloral-phosphite ester condensation product; said condensation productbeing prepared by mixing together 1 mol of chloral and 1 mol of aphosphite ester of the general formula Rr-X wherein each of R and Rrepresents a radical selected from the group consisting of saturatedaliphatic hydrocarbon radicals containing 1 to 4 carbon atoms, phenylradicals and chlorinated phenyl radicals, R represents a saturatedaliphatic radical containing 1 to 4 carbon atoms,

member selected from the group nitrogen and sulfur, and Z is a memberselected from the group consisting of oxygen" and sulfur, an organicsolvent boiling at atmospheric pressure below 200 C., and an noni'onogenic emulsiiying agent.

9. An insecticidal composition of matter which consists of 20 parts byweight of a trimethyl phosphite-chloral condensation product, saidcondensation product being prepared by mixing together equimolecularproportions of trimethyl phosphite and chloral, 40 parts by wei ht ofthe condensation product from 1 mol of octyl phenol with 8 mols ofethylene oxide, and 40 parts by weight of n-butanol.

10. An insecticidal dusting powder which consists of a chloral-phosphiteester condensation product said condensation product being prepared byadding together 1 mol of chloral and 1 mol of a phosphite ester of thegeneral formula X and Y are each a consisting of oxygen,

wherein each of R and R represents a radical selected from the groupconsisting of saturated aliphatic hydrocarbon radicals containing 1 to 4carbon atoms, phenyl radicals and chlorinated phenyl radicals, Rrepresents a saturated aliphatic radical containing 1 to 4 carbon atoms,X and Y are each a member selected from the group consisting of oxygen,nitrogen and sulfur, and Z is a member selected from the groupconsisting of oxygen and sulfur, and a powdered inert carrier.

11. An insecticidal dusting powder which consists of 0.1 to 10 percentby Weight of a trimethyl phosphitechloral condensation product, saidcondensation product being prepared by adding together equimolecularproportions of trimethyl phosphite and chloral, and 99.9 to 90 percentby weight of a powdered inert carrier.

2,579,810 Fields Dec. 25, 1951 UNITED STATES PATENT OFFICE CER'IIFICATE0F CORRECTION Patent No. 2,861,912 November 25, 1958 Richard Sallmann Itis hereby certified that error appears in the printed specification ofthe above numbered patent requiring correction and" that the saidLetters Patent should read as corrected below.

1 Column 1, line 52, for "radicas read me radicals. line '72, for "andread the column 5, line 24, for "0,0" read 0.04 line '74, for Examples"read M Example Signed and sealed this 2nd day of June" 1959,

(SEAL) Attest:

KARL N ROBERT c. WATSON Attesting Officer Conmissioner of Patents Noticeof Adverse Decision in Interference In Interference No. 90,243 involvingPatent No. 2,861,912, R. Sallmann,

Method for combating pests and preparatlons sultable therefor, finaljudgment adversif to the patentee was rendered Sept. 6, 1962, as toclaims 1, 2, 3, 4, 5, 7 8, 10 an 11.

[Ofiioz'al Gazette J anmwy Q9, 1963.]

1. A METHOD FOR COMBATING INSECTS WHICH COMPRISES APPLYING TO THEOBJECTS WHICH ARE TO BE PROTECTED AGAINST THE INSECTS AN INSECTICIDALAMOUNT OF A CHLORAL-PHOSPHITE ESTER CONDENSATION PRODUCT SAID PRODUCTBEING PREPARED BY ADDING TOGETHER 1 MOL OF CHLORAL AND 1 MOL OF APHOSPHITE ESTER OF THE GENERAL FORMULA